B-doped p-BaSi2 epitaxial layers with a hole concentration of 1.1 × 1018 cm−3 were grown on n-Si(001) using molecular beam epitaxy to fabricate p-BaSi2/n-Si solar cells. The thickness (d) of the p-BaSi2 layer was varied from 20 to 60 nm to investigate its effect on the solar cell performance. The conversion efficiency under an AM1.5 illumination increased with d reaching a maximum of 9.8% at d = 40 nm, which is nearly equal to the highest efficiency (9.9%) for p-BaSi2/n-Si solar cells on Si(111). This study indicated that Si(001) substrates are promising for use in BaSi2 solar cells.